Detailed Description
Embodiments of the present application will be described below with reference to the accompanying drawings.
Conventionally, a rear cover of an electronic device such as a mobile phone generally adopts a glass product with a superhard film on one side, and the structure of the glass product 100 is as shown in fig. 1, and the glass product comprises a glass substrate 10, and the superhard film 20 is disposed on one side (specifically, the outer side facing the outside of the electronic device) of the glass substrate 10. Since only one side of the glass article 100 has a film layer with higher hardness and the other side has no film layer with higher hardness to balance, the strength of the glass article 100 is significantly reduced compared with that of the glass substrate 10, the strength reduction percentage is more than 30%, and the impact resistance (such as poor drop resistance) of the glass article 100 is seriously reduced. In addition, in order to achieve higher brightness of the glass product 100, the thickness of the superhard film 20 is generally thicker than 1 μm, the manufacturing cost is higher, and the color decoration range of the excessively thick superhard film 20 is narrow, resulting in poor color adjustability of the glass product 100. In order to solve the problems of the existing glass products, the embodiment of the application provides a glass product which has good wear resistance, high strength, low thickness and wide color adjustability.
Referring to fig. 2, fig. 2 is a schematic structural view of a glass product according to an embodiment of the present application. The glass product 200 provided by the embodiment of the application comprises a glass substrate 10, wherein the glass substrate 10 is provided with a first surface 101 and a second surface 102 which are arranged oppositely, the first surface 101 is provided with a superhard film 20, and the second surface 102 is provided with a brightness enhancement film 50. Wherein the reflectance of the brightness enhancement film 50 is greater than or equal to 25% and the transmittance of the superhard film 20 is greater than or equal to 50%. Obviously, the effect of the brightness enhancement film 50 is different from that of the superhard film 20, the superhard film 20 has higher light transmittance except higher hardness, and the brightness enhancement film 50 has higher reflectivity and poorer light transmittance.
When the glass article 200 is used as a housing of an electronic device, such as a rear cover, the first surface 101 faces the exterior of the electronic device ("exterior" specifically refers to the portion that can be directly contacted or viewed by a user) and the second surface 102 faces the interior of the electronic device, so that the first surface 101 may be referred to as an "exterior surface" and the second surface 102 may be referred to as an "interior surface". Accordingly, the superhard film 20 faces the exterior of the electronic device and the brightness enhancing film 50 faces the interior of the electronic device.
According to the application, the superhard films 20 are arranged on the outer surface of the glass substrate 10, and the brightness enhancement films 50 are arranged on the inner surface, on one hand, by means of the cooperation of the brightness enhancement films 50 and the brightness enhancement films 50 on the two sides of the glass substrate, the influence of the stress of the unilateral superhard films on the reduction of the glass strength can be reduced under the condition that the wear resistance of the glass product 200 is still higher, and the stress on the two sides of the glass substrate is balanced, so that the strength of the glass product 200 is relatively higher, and the impact resistance of the glass product is better. On the other hand, the brightness enhancement film 50 with high reflectivity is introduced to significantly increase the brightness of the glass product 200, specifically, when light is injected from the outside of the glass product 200, after passing through the super-hard film 20 with high transmittance and the glass substrate 10, after being reflected by the brightness enhancement film 50 with high reflectivity, more light passes through the glass substrate 10 and the super-hard film 20 to enter the human eye, and the brightness of the glass product 200 seen by the human eye is higher. In the case where the glass article 200 of the embodiment of the present application achieves the same brightness as the existing glass article 100, the thickness of the superhard film 20 in the glass article 200 of the embodiment of the present application is significantly lower than the thickness of the superhard film 20 in the existing glass article 100. The manufacturing cost of the superhard film 20 in the glass product 200 is reduced, the superhard film 20 with lower thickness is not easy to warp, the stability of a film layer is improved, the thickness of the superhard film 20 is reduced, the reflection curve of the superhard film 20 is smoother during film system design, the color stability is better, the color of the glass product 200 can be conveniently regulated and controlled by the superhard film, and the color adjustable range of the glass product 200 is widened. In addition, the thickness of the superhard film 20 is reduced, which is advantageous for properly reducing the overall thickness of the glass product 200 compared with the glass product 100, and further for manufacturing a light and thin electronic device housing.
Therefore, the glass product 200 provided by the embodiment of the application can have the advantages of high hardness (good wear resistance), high strength, low thickness, wide color adjustability and the like. The glass product 200 is suitable for manufacturing electronic equipment with good mechanical properties and high aesthetic degree.
In the present application, the reflectivity of the brightness enhancement film 50 is controlled to be greater than or equal to 25% in order to ensure the brightness enhancement effect of the brightness enhancement film 50 on the color, and to avoid weakening the brightness enhancement effect due to low reflectivity of the brightness enhancement film 50. In addition, the light transmittance (specifically, the light transmittance to visible light) of the superhard film 20 is controlled to be greater than or equal to 50%, so as to ensure that the loss of light in the process of passing through the superhard film 20 is not too low, and avoid the brightness enhancement effect of the light reflected from the brightness enhancement film 50 from being reduced after passing through the superhard film 20. In some embodiments of the present application, the reflectance of the brightness enhancement film 50 is 30% or more, and further may be 40% or more, or 50% or more, or 60% or more, or 70% or more, or the like. The visible light transmittance of the superhard film 20 is 55% or more, 60% or more, or 70% or more, or 80% or more, or 90% or more, or the like. In addition, the visible light transmittance of the brightness enhancing film 50 is less than 50%.
In the embodiment of the present application, the pencil hardness of the brightening film 50 is 5H or more. The brightness enhancing film 50 has a relatively high hardness and, when disposed on the opposite side of the glass substrate from the superhard film 20, better counteracts the effect of the stress of the single-sided superhard film on the strength of the glass. Wherein the word "pencil hardness" is a scratch hardness measured according to a pencil test of coating hardness.
In the present application, the superhard film 20 has a hardness greater than that of the brightness enhancing film 50 under the same hardness comparison standard. In the embodiment of the application, the pencil hardness of the superhard film 20 can be 9H, and the Mohs hardness of the superhard film 20 can be more than 7. The superhard film 20 on the outside of the glass substrate has a relatively high hardness so as to ensure excellent wear resistance of the glass article 200. The word "Mohs hardness" is also called scratch hardness, which is a relative hardness, 10 natural minerals are selected as standards, the hardness sequence does not represent the determined size of the hardness value of the object to be measured, and only the minerals with high hardness sequence can scratch the minerals with low hardness sequence. The hardness of other minerals is determined by comparing the standard minerals with each other by scoring. In the present application, mohs hardness is measured by scoring the surface of an article being tested with a pyramid-shaped diamond drill of known hardness using a scoring method.
In an embodiment of the present application, the percent decrease in flexural strength of the glass article 100 as measured based on the four-point bending test method is 20% or less compared to the flexural strength of the glass substrate 10 without the brightness enhancing film 50 and the superhard film 20. For example, when the bending strength of the glass product 100 is denoted as a MPa, the bending strength of the glass substrate 10 alone is denoted as b MPa, and the above-described percentage drop is denoted as k, k= (b-a)/bx 100%. In some embodiments, the percentage decrease is below 15%, further below 12%, or below 11%, or below 10%.
In the embodiment of the present application, the bending strength of the glass product 100 measured by the four-point bending test method may be 490MPa or more, and further may be 510MPa or more, or 530MPa or more, or 535MPa or more, or 540MPa or more, or the like.
In the embodiment of the application, based on a four-point bending test method, the glass product is not broken when the bending load applied to the glass product is more than or equal to 300N. This indicates that the mechanical strength of the glass article is high.
In some embodiments of the application, the thickness d1 of the brightness enhancing film 50 and the thickness d2 of the superhard film 20 satisfy the relationship that 0.4d2≤d1＜d2.d1 and d2 are in the same units. The brightness enhancement film 50 having a thickness satisfying this relationship is provided on the other side of the glass substrate opposite to the superhard film 20, and the influence of the stress of the single-sided superhard film on the strength of the glass can be well offset. In this case, the percent decrease in the bending strength of the glass article 100 as compared to the bending strength of the glass substrate 10 is 15% or less, as measured on the basis of the four-point bending test method. Wherein the bending strength of the glass product 100 may be 510MPa or more, and further 530MPa or more. In some embodiments, d1/d2 can be in the range of 0.5-0.95, such as specifically 0.55, 0.60, 0.65, 0.68, 0.70, 0.72, 0.75, 0.80, or 0.90, etc.
In an embodiment of the present application, in order to ensure high hardness and good wear resistance of the superhard film 20, the thickness d2 of the superhard film 20 may be 600nm or more. In some embodiments, the thickness d2 of the superhard film 20 may be in the range 600nm to 950 nm. The superhard film 20 with proper thickness can increase the brightness of the glass product 200 and increase the color adjustable range by matching with the brightness enhancement film 50 while ensuring higher hardness and more stable film layer structure of the glass product 200. Illustratively, d2 may be specifically 620nm, 640nm, 660nm, 680nm, 700nm, 720nm, 750nm, 800nm, 820nm, 850nm, 900nm, 950nm, etc. In some embodiments, d2 may be in the range of 600-900nm, and further may be in the range of 600-860 nm.
In some embodiments of the present application, the thickness d1 of the brightness enhancing film 50 may be in the range of 240-600 nm. The brightness enhancement film 50 with proper thickness can better offset the stress generated by the outer plating of the superhard film on one side while ensuring the brightness of the glass product 100, thereby enhancing the strength of the glass product.
In an embodiment of the present application, the brightness enhancement film 50 includes a laminated structure in which first high refractive index material layers and first low refractive index material layers are alternately stacked. In other words, the brightness enhancement film 50 includes at least one first high refractive index material layer (abbreviated as a layer) and at least one first low refractive index material layer (abbreviated as B layer), and the a layer and the B layer are alternately laminated. It is understood that the refractive index of the a layer is greater than that of the B layer. The laminated structure of the brightness enhancing film 50 may be an arrangement of (A-B)n, or (B-A)n, or (A-B)n -A, or (B-A)n -B (n is an integer of 1 or more) from the glass substrate 10 toward the brightness enhancing film 50. The thickness of each a layer may be the same or different. The thickness of each B layer may be the same or different.
In embodiments of the present application, the refractive index of the a layer may be greater than or equal to 2.0 and the refractive index of the b layer may be less than or equal to 1.55. Wherein, the A layer can comprise one of a niobium pentoxide layer (namely a Nb2O5 layer), a titanium dioxide layer (namely a TiO2 layer), a titanium pentoxide layer (namely a Ti3O5 layer), a niobium nitride layer (namely a NbN layer) or a titanium boride layer (namely a TiB layer). Wherein the B layer may include one of a silicon dioxide layer (i.e., siO2 layer), an aluminum oxide layer (i.e., al2O3 layer), a magnesium fluoride layer (i.e., mgF2 layer).
In some embodiments of the present application, the layer a is a niobium pentoxide layer and the layer B is a silicon dioxide layer. The high refractive index material in the brightness enhancement film 50 adopts Nb2O5, and has higher refractive index, generally about 2.3, difficult change of refractive index, stable performance and small absorption coefficient, thereby being beneficial to ensuring that the brightness enhancement film 50 meets the optical design requirement. The low refractive index material of the brightness enhancement film 50 is SiO2, which has a low refractive index of about 1.45, and the manufacturing cost of SiO2 is low.
In some embodiments of the present application, the brightness enhancement film 50 further includes an indium layer (i.e., in layer), where the presence of the indium layer enhances the reflective effect of the brightness enhancement film 50. Wherein the indium layer is located between any adjacent first high refractive index material layer (layer a) and first low refractive index material layer (layer B). For example, in some embodiments, the brightness enhancing film 50 includes two a layers and two B layers, the a layers and the B layers being alternately stacked, the a layers being in contact with the glass substrate 10. The indium layer may be located between the 1 st a layer and the 1 st B layer, or between the 1 st B layer and the 2 nd a layer, or between the 2 nd a layer and the 2 nd B layer, from the glass substrate 10 toward the brightness enhancing film 50. If the indium layer is referred to as layer C, the brightness enhancing film 50 may be specifically in the form of an arrangement of A-C-B-A-B, or A-B-C-A-B, or A-B-A-C-B, from the glass substrate 10 toward the brightness enhancing film 50.
In an embodiment of the present application, the superhard film 20 comprises a laminated structure of alternating layers of a first superhard high refractive index material layer (referred to as a D layer for short) and a second low refractive index material layer (referred to as an E layer for short). It is understood that the refractive index of the D layer is greater than that of the E layer. In other words, the superhard film 20 comprises at least one D layer and at least one E layer, the D layer and the E layer being alternately laminated, the refractive index of the D layer being greater than the refractive index of the E layer. The laminated structure of the superhard film 20 may be an arrangement of (D-E)n, or (E-D)n, or (D-E)n -D, or (E-D)n -E (n is an integer of 1 or more) from the glass substrate 10 toward the superhard film 20. The thickness of each D layer may be the same or different. The thickness of each E layer may be the same or different.
In an embodiment of the present application, the refractive index of the D layer may be greater than or equal to 1.65, and the refractive index of the E layer is less than or equal to 1.55. Wherein the E layer may include a silicon dioxide layer (i.e., siO2 layer) or an aluminum oxide layer (i.e., al2O3 layer). The D layer may include one of a silicon nitride layer (SiNx layer), a zirconium dioxide layer (i.e., zrO2 layer), an aluminum nitride layer (AlNx layer), a silicon oxynitride layer (i.e., siON layer), or an aluminum oxynitride layer (i.e., alON layer). The refractive indexes of the silicon oxynitride layer and the aluminum oxynitride layer can be more than or equal to 1.65, and the refractive indexes of the silicon nitride layer, the zirconium dioxide layer and the aluminum nitride layer can be more than or equal to 1.85.
In some embodiments of the present application, the D layer is a silicon nitride layer and the E layer is a silicon dioxide layer. The superhard film 20 is made of silicon nitride (refractive index is generally about 1.95), and has high hardness, excellent wear resistance and stable chemical properties, and can effectively increase the hardness and wear resistance of the superhard film 20. The low refractive index material of the brightness enhancement film 50 is SiO2, which has a low refractive index of about 1.45 and low manufacturing cost.
Wherein, the layer A, the layer B, the layer D and the layer E can be independently plated by chemical vapor deposition, or physical vapor deposition, wherein the chemical vapor deposition comprises but is not limited to hot filament chemical vapor deposition, or plasma enhanced chemical vapor deposition, etc. Physical vapor deposition includes, but is not limited to, magnetron sputtering, vacuum evaporation, ion plating (e.g., arc ion plating, radio frequency ion plating), and the like. In some embodiments of the application, the A layer, the B layer, the D layer and the E layer are all plated by magnetron sputtering. An exemplary plating process is that the reactive gas for forming the film layer and the sputter protecting gas can be filled into the vacuum deposition cavity and ionized, and the ionization can bombard the surface of the sputter target material under the action of a strong magnetic field so as to deposit and form a corresponding film layer on the surface of the substrate to be plated. In addition, ICP (Inductively Coupled Plasma ) can be adopted for auxiliary coating in the magnetron sputtering process so as to improve the bonding force of the film layer. The thickness, performance and the like of the film can be regulated and controlled by adjusting parameters such as pressure in the deposition cavity, temperature of a substrate to be plated, magnetron sputtering speed, target power, flow rates of reaction gas and sputtering gas, ICP power and the like.
In the embodiment of the present application, the thickness of the glass substrate 10 may be in the range of 0.4mm to 1.0mm, for example, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, etc. are specific examples. The glass substrate 10 is a substrate of the glass product 200, and serves to support the superhard film 20, the brightness enhancement film 50, and the like. The glass substrate 10 may be silicate glass, borate glass, phosphate glass, or the like. In addition, these glass substrates may be specifically chemically strengthened glass substrates to provide their protective effect for use as housings for electronic devices.
In some embodiments of the application, as shown in fig. 3, the side of the superhard film 20 facing away from the glass substrate 10 is further provided with an Anti-fingerprint (AF) layer 30. That is, the superhard film 20 and the anti-fingerprint layer 30 are sequentially laminated on the first surface 101. The fingerprint-resistant layer 30 is mainly used for reducing fingerprint formation on the glass product 200 when a user touches the glass product 200, so that the appearance effect of the glass product 200 is not affected. Wherein the thickness of the anti-fingerprint layer 30 may be in the range of 5nm to 30 nm.
In some embodiments of the present application, as shown in FIG. 3, the side of the brightness enhancing film 50 facing away from the glass substrate 10 is also provided with an ink layer 40. The ink layer 40 mainly plays a role of masking, for example, a flat cable structure which is arranged on the inner side of the glass product 200 in a subsequent manner, and the visual effect of the glass product 200 is improved. The ink layer 40 may be provided by screen printing or ink jet printing, and the ink layer 40 may be a complete film or an array of films. In addition, the color of the ink layer 40 may include, but is not limited to, red, orange, yellow, green, cyan, blue, violet, black, and the like. Any different colors can be selected to meet different use requirements. In some embodiments, the ink layer 40 is black in color. The location, thickness, color, etc. of the ink layer 40 may be adjusted according to the desired visual effect of the glass article 200. Illustratively, the thickness of the ink layer 40 may be in the range of 10 μm to 50 μm.
Referring to fig. 4, fig. 4 is a schematic structural view of a glass product according to another embodiment of the present application. The glass article of fig. 4 differs from the glass article of fig. 3 described above in that the glass article 200 of fig. 4 further includes a support film 60, the support film 60 being positioned between the brightness enhancing film 50 and the ink layer 40.
The support film 60 may be specifically used to support the ink layer 40, for example, the ink layer 40 may be formed on one side of the support film 60, and then the other side of the support film 60 is bonded to the glass substrate 10 with the superhard film 20 and the brightness enhancement film 50 on the opposite sides. In the embodiment of the present application, the material of the support film 60 may include polyethylene terephthalate (polyethylene terephthalate, PET), polyimide (PI), or the like. In addition, to facilitate a secure attachment between the support film 60 and the glass substrate 10 with the superhard film 20 and the brightness enhancing film 50 on opposite sides thereof, the surface of the support film 60 may be provided with an adhesive layer, such as OCA (Optically CLEAR ADHESIVE) optical or pressure sensitive adhesive. Wherein the thickness of the support film 60 may be in the range of 0.1mm to 0.5 mm.
In the glass product 200 shown in fig. 4, the superhard film 20 and the brightness enhancing film 50 are provided on opposite sides of the glass substrate 10, respectively, and effects similar to those of the glass product shown in fig. 2 can be obtained. That is, by coating the superhard film on the outer side and coating the brightness enhancement film on the inner side, the effect of the stress of the superhard film on the glass strength on the single side can be counteracted by the brightness enhancement film 50, so that the strength of the glass product 200 is ensured not to be obviously reduced compared with that of the uncoated glass substrate, the thickness of the superhard film can be reduced, and the color adjustable range of the glass product 200 can be increased. For the superhard film 20, the anti-fingerprint layer 30, the brightness enhancing film 50, and the ink layer 40, reference is made to the description of the application above.
Referring to fig. 5, fig. 5 is a schematic structural view of a glass product according to another embodiment of the present application. Fig. 5 differs from the glass article of fig. 3 described above in that the glass article 200 of fig. 5 further includes a support film 60, the support film 60 being positioned between the glass substrate 10 and the brightness enhancing film 50.
The support film 60 in fig. 5 may be used to support the brightness enhancing film 50 and the ink layer 40. For example, the brightening film 50 may be coated on a first side of the support film 60, the ink layer 40 may be formed by printing, and then the second side (opposite to the first side) of the support film 60 may be bonded to the glass substrate 10 having the superhard film 20 formed on one side, and the superhard film 20 and the support film 60 may be positioned on opposite sides of the glass substrate 10. Similarly, to facilitate a secure fit of the support film 60 to the glass substrate 10, the surface of the support film 60 may be provided with an adhesive layer, such as OCA or pressure sensitive adhesive.
In the glass product 200 shown in fig. 5, the superhard film 20 and the brightness enhancing film 50 are provided on opposite sides of the glass substrate 10, respectively, and effects similar to those of the glass product shown in fig. 2 can be obtained. For the superhard film 20, the anti-fingerprint layer 30, the brightness enhancing film 50, and the ink layer 40, reference is made to the description of the application above.
In the application, a simulation model machine consisting of each glass product and 200g of counterweight is placed in a vibration abrasion-resistant instrument provided with abrasive particles, more than half of the machine body of the simulation model machine is kept to be immersed in the abrasive particles, abrasion resistance test is carried out for more than 120min under the vibration frequency of 5050+/-0.5 HZ, and the surface of the glass product is free from obvious abrasion and bruise. This shows that the wear resistance of the glass product is better, and the application prospect is good. Wherein, when the above-mentioned simulation prototype is prepared by using a glass product, a weight of 200g is provided on one side of the brightness enhancement film thereof.
In some embodiments of the application, the thickness of each glass article 100 described above may be in the range of 0.05mm to 0.2 mm. In this case, the glass article may still have a bending radius of less than or equal to 5mm. This shows that thinner glass articles with the superhard film 20 and the brightness enhancing film 50 described above can still have good bending properties and can be used to make ultra thin flexible glass (UTG) for foldable electronic devices. And each film layer of the glass product has no chapping, breakage, falling off and the like. Specifically, the thickness of the glass article 100 may be specifically 0.06mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.2mm, or the like. Further, in this case, the glass article was not broken when a bending load of 300N or more was applied thereto based on the four-point bending test method.
The embodiment of the application also provides electronic equipment, and the shell of the electronic equipment can comprise the glass product. Referring to fig. 6A and fig. 6B together, fig. 6A is a schematic perspective view of an electronic device 300 according to an embodiment of the application, and fig. 6B is a schematic rear-side structure of the electronic device in fig. 6A. The electronic device 300 may be a mobile phone, a tablet computer, a notebook computer, a wearable device (such as a smart watch, a smart bracelet, etc.), an augmented Reality (Augmented Reality, AR) device, a Virtual Reality (VR) device, an in-vehicle device, etc., which is not limited in this regard. The present embodiment is described taking the electronic device 300 as an example of a mobile phone.
The electronic device 300 may include a housing 31 assembled outside the electronic device, and a circuit board (not shown) located inside the housing 31. The electronic device 300 may further include a display module 32, where the display module 32 is connected to the housing 31, and specifically the display module 32 may be mounted on the housing 31. Wherein the housing 31 includes a rear cover 311 assembled at the rear side of the electronic device 300. The rear cover 311 may cover only the rear side of the electronic device 300 (i.e., the side facing away from the display module 32), or may cover both the rear side and the side frame of the electronic device 300. In the embodiment of the present application, the rear cover 311 may be manufactured using the glass product 200 according to the embodiment of the present application, may be manufactured using the glass product 200 entirely, or may be manufactured using the glass product 200 only partially. When the rear cover 311 is manufactured by using the glass product 200, the ink layer 40 of the glass product 200 faces the display module 32 and the anti-fingerprint layer 30 faces away from the display module 32.
In some embodiments of the present application, as shown in fig. 6B, the electronic device 300 further includes a camera module 33 disposed inside the housing 31, where the housing may include a camera protection cover 312, and the camera protection cover 312 is disposed on the camera module 33 and used for protecting the camera module 33, and the camera protection cover 312 may be made of the glass product 200 according to the embodiment of the present application, specifically may be made of all the glass product 200, or may be made of only part of the glass product 200.
The rear cover 311 and/or the camera protective cover 312 of the electronic device 300 may use the glass product 200 according to the embodiment of the present application, and may have good wear resistance, mechanical strength, and gorgeous appearance of color tone, so that market competitiveness of the electronic device is outstanding.
The technical scheme of the application is described in detail below with reference to specific embodiments.
Example 1
A glass product has a structure shown in figure 2, and comprises a glass substrate 10 with the thickness of 0.55mm, wherein a superhard film 20 is arranged on the first surface 101 of the glass substrate 10, the total thickness d2 is 640nm, and the glass product is specifically 6 film layers formed by alternately stacking silicon nitride layers and SiO2 layers, wherein 3 layers are respectively arranged on the silicon nitride layers and the SiO2 layers, and the SiO2 layers are directly adhered to the glass substrate 10. The second surface 102 of the glass substrate 10 is provided with a brightness enhancement film 50, the total thickness d1 is 440nm, specifically, 4 film layers formed by alternately stacking Nb2O5 layers and SiO2 layers, wherein 2 layers are respectively arranged on the Nb2O5 layers and the SiO2 layers, and the Nb2O5 layers are directly adhered to the glass substrate 10.
In example 1, the visible light transmittance of the superhard film 20 was 62%, and the reflectance of the brightness enhancement film 50 was 35%. d1/d2 =0.68.
Example 2
The difference from the glass article of example 1 is that the ratio of the total thickness d1 of the brightness enhancing film 50 to the thickness d2 of the superhard film 20 is 0.4. In the glass product of example 2, the total thickness d2 of the superhard film was 850nm, the total thickness d1 of the brightness enhancement film 50 was 340nm, and the number of layers and the film layer structure were the same as those of example 1.
Example 3
The difference from the glass article of example 1 is that the ratio of the total thickness d1 of the brightness enhancing film 50 to the thickness d2 of the superhard film 20 is 0.9. The glass product of example 3 has a total thickness d2 of 600nm, the film layer structure of which is the same as that of example 1, and the total thickness d1 of the brightness enhancement film 50 is 540nm, which is specifically 9 film layers formed by alternately stacking Nb2O5 layers and SiO2 layers, wherein 4 layers are provided on the Nb2O5 layer, 5 layers are provided on the SiO2 layer, and the SiO2 layer is directly adhered on the glass substrate 10.
Example 4
The difference from the glass article of example 1 is that the ratio of the total thickness d1 of the brightness enhancing film to the thickness d2 of the superhard film is specifically 0.29, less than 0.4. In the glass product of example 4, the total thickness d1 of the brightness enhancement film 50 is 187nm, which is specifically 7 film layers formed by alternately stacking Nb2O5 layers and SiO2 layers, wherein 3 layers are provided for Nb2O5 layers, 4 layers are provided for SiO2 layers, and the SiO2 layers are directly adhered to the glass substrate 10.
Example 5
The difference from the glass product of example 1 is that the brightness enhancement film 50 is specifically a 4-layer film layer formed by alternately stacking Ti3O5 layers and SiO2 layers, 2 layers are respectively formed on the Ti3O5 layer and the SiO2 layer, and the Ti3O5 layer is directly adhered to the glass substrate 10. The total thickness d1 of the brightness enhancement film 50 was 271nm. d1/d2 =0.42.
To highlight the advantageous effects of the present application, the following comparative examples are set forth.
Comparative example 1
A glass article, specifically a glass substrate for example 1, was not provided with any film layer on its surface.
Comparative example 2
A glass product has a structure shown in FIG. 1, and comprises a glass substrate 10 (same as in example 1), wherein one side of the glass substrate 10 is provided with a superhard film 20, the total thickness of the superhard film is 1100nm, and the superhard film is specifically 10 film layers formed by alternately stacking silicon nitride layers and SiO2 layers, wherein 5 layers are respectively arranged on the silicon nitride layers and the SiO2 layers, and the SiO2 layers are directly adhered to the glass substrate 10. The visible light transmittance of the superhard film was 53%.
To advantageously support the benefits of the present application, the following performance tests were performed on the glass articles of the examples and comparative examples described above:
a. Hardness test the surface of the glass article to be measured (specifically, the superhard film thereof was scored for each of examples and comparative example 2) was scored using a pyramid diamond needle by scoring, and the depth of the score, which is mohs hardness, was measured.
As a result, it was found that the Mohs hardness of the superhard films in the glass products of each of examples and comparative example 2 could reach 8, whereas the Mohs hardness of the mere glass substrate (comparative example 1) was only 5.
B. Abrasion resistance test:
The testing equipment is a vibration abrasion-resistant instrument R180/530E 30 (the equipment frequency is 50+/-0.5 HZ, and the amplitude is 1.65+/-0.1 mm). 15 liters of mixed abrasive including 3 parts by volume of RKF 10K (yellow cylindrical abrasive particles) and 1 part by volume of RKK P (green cone abrasive particles) was used.
Test sample preparation the glass articles of the examples and comparative examples were held together with 200g of a weight (for the examples and comparative example 2, the weight was disposed on the side of the glass substrate facing away from the superhard film) to form a simulated prototype, which was placed in a vibration abrasion tester for testing. Wherein, each vibration wear-resisting instrument is put into 2 simulation prototypes at most to avoid collision.
The test procedure was as follows (1) 1L of water was poured uniformly into a vibration tank containing the above abrasive in a vibration-resistant apparatus so that the abrasive remained wet, and 200mL of a detergent (the detergent was obtained from commercial Germany)The test liquid medicine FC120 of the vibration abrasion-resistant machine is diluted according to the volume ratio of 1:50) so as to play a role of lubrication, and (2) the test sample machine is numbered and placed in a vibration groove filled with mixed abrasive materials, so that the uniform head of the simulation sample machine is inserted upwards into the abrasive materials, at least half of the machine body of the simulation sample machine is ensured to be immersed into the abrasive materials, and a vibration abrasion-resistant instrument is started to serve as a timing zero point. And (3) uniformly pouring about 500mL of water into the vibration tank to ensure that the abrasive is kept wet continuously, repeating the step (2), and taking out the sample machine for observation and photographing at 60min, 90min and 120min respectively.
As a result, it was found that after the abrasion resistance test was performed for 120min (i.e., 2 hours), the glass products of each example and comparative example 2 were free from significant abrasion and bruise on the large face and the corners, and the film layer was free from peeling and bottom leakage, which indicates that the abrasion resistance of the superhard film in the glass product was good, and that the surface of the glass product of comparative example 1 was severely scratched.
C. Glass strength test:
The glass strength was tested based on the four-point bending test, and a schematic diagram is shown in fig. 7. The test method comprises the following steps:
① Processing each glass product into a 3D curved sample, and checking the appearance of each glass sample before testing to ensure that the product has no influence on strength defects such as cracks, gaps and the like;
② The support (below the lower supporting roller) and the upper pressing roller of the checking and cleaning strength tester ensure that the upper and lower rollers are clean and the surface is free from serious scratches;
③ Fixing a test sample by adopting a four-point bending test fixture, so that the test sample is positioned between an upper pressing roller and a lower supporting roller and is positioned at the middle position of the two lower supporting rollers (shown in figure 7), wherein the measuring direction of the test sample and the upper and lower rollers are selected as follows, 3D curved surface products are measured in the Y-axis direction (the length direction of the products), and the diameters of the lower supporting roller and the upper pressing roller are 6mm;
④ Setting a preload, generally 1-2N, to ensure that the test sample contacts the upper and lower rollers;
⑤ Setting the pressing speed of the load to be 10mm/min;
⑥ Starting a testing instrument, starting to apply bending load, continuously applying the bending load at the pressing speed of 10mm/min until the test sample breaks, and recording the maximum load value applied in the testing process, namely the maximum load F corresponding to the breaking moment of the sample;
⑦ The bending strength was calculated according to the following formula:
σ=3F×(Ls-Lb)/(2B×H2)
Wherein sigma represents the bending strength of the test sample in MPa;
f represents the corresponding maximum load when the test sample breaks, and the unit is N;
Ls represents the distance between the central lines of the two lower support rollers, and the unit is mm, in the application, ls is 40mm;
Lb represents the distance between the central lines of the two upper press rolls, wherein the unit is mm, and in the application, lb is 20mm;
b represents the width (parallel to the extension direction of each roller) of the test specimen in mm;
h represents the thickness of the test sample in mm.
⑧ Each group was tested for 5 parallel samples and the measured 5 flexural strengths were averaged, the test results being shown in table 1 below.
TABLE 1
As can be seen from Table 1, the glass product of comparative example 2, in which the superhard film was provided on one side of the glass substrate, had a severe decrease in bending strength of about 30.1% as compared with the glass substrate (comparative example 1). In the embodiment of the application, after the superhard film is arranged on one side of the glass substrate and the brightness enhancement film is arranged on the opposite side of the glass substrate, the bending strength of the obtained glass product is still higher, and the bending strength of the glass product is reduced by less than 20% compared with that of the glass substrate, wherein the bending strength of the glass products in the embodiments 1-5 is reduced by 8.48%, 11.17%, 5.81%, 19.09% and 9.69% respectively compared with that of the glass substrate. From the comparison between examples 1-4, when the ratio of the thickness d1 of the brightness enhancing film to the thickness d2 of the superhard film in the glass article is less than 0.4 (this ratio is 0.29 in example 4), the percent strength drop of the glass article compared to the glass substrate is relatively high.
In addition, the glass products of comparative example 2 and example 1 were also subjected to a reflectivity test, specifically, white light was irradiated from the side of the superhard film, the angle of incidence of the white light was controlled to be 10 ° with respect to the linear direction of the superhard film, and the measured reflection curves are shown in fig. 8A and 8B, respectively.
As can be seen from fig. 8A and 8B, the comparative example 2 glass product with the superhard film coated on one side and the example 1 glass product with the superhard film coated on the outer side and the brightness enhancement film coated on the inner side can achieve substantially the same Lab chromaticity coordinate values (the Lab chromaticity coordinate of comparative example 2 has a value of 12.18, a value of 28.37 and an l value of 69.47, and the Lab chromaticity coordinate of example 1 has a value of 12.18, B value of 28.40 and an l value of 69.47), and the reflection curve of the glass product of example 1 is smoother, which reflects better color stability. It should be noted that in the case where the two reach a near color effect, the thickness of the superhard film itself in comparative example 2 is 1100nm, whereas the thickness of the superhard film in example 1 of the present application is only 640nm, and the total thickness of the superhard film and the brightness enhancing film is 1080nm. It can be seen that the thickness of the superhard film in the embodiment of the application is obviously lower and is more beneficial to color adjustment under the condition that the glass product with the superhard film coated on one side of the comparative example achieves the same brightness/color as the glass product in the embodiment of the application.
In addition, the glass articles of examples 2-5 also had substantially the same color effect as example 1, and their reflection curves were similar.
As a result, the superhard films are arranged on one of the two opposite sides of the glass product, and the brightness enhancement film is arranged on one side of the superhard films, so that the glass product has good wear resistance, the strength is not obviously reduced, the mechanical property is excellent, and meanwhile, the thickness of the superhard films in the glass product is relatively low, so that the appearance color of the glass product can be conveniently adjusted.
While the foregoing is directed to exemplary embodiments of the present application, it will be appreciated by those skilled in the art that various modifications and adaptations can be made thereto without departing from the principles of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the present application.
It should be noted that, unless explicitly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected, mechanically connected, directly connected, indirectly connected via an intermediate medium, or in communication between two elements. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
Directional terms, such as "upper", "lower", "front", "rear", "left", "right", "inner", "outer", "side", etc., in the present application are merely referring to the directions of the attached drawings, and thus, directional terms are used for better, more clear explanation and understanding of the present application, rather than indicating or implying that the apparatus or element being referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present application.
Furthermore, in the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more. In the present specification, the numerical range indicated by "-" means a range in which numerical values described before and after "-" are included as a minimum value and a maximum value, respectively. In the drawings, like or structurally similar elements are denoted by like reference numerals.